Method of making microporous structure defined by a multiplicity of singular channels

ABSTRACT

A microporous structure can be formed from ductile material such as glass into an axially extended outer wall surrounding a plurality of singular micro-passages surrounded by the outer wall to provide an open area that extends continuously over the length of the outer wall. The diameter of the micro-passages will usually not exceed 25 μm and are more in range of from 0.5 to 5 μm. The structure is particularly useful as frits for the containment of packing in capillaries for chromatograph applications and more generally as flow restrictors. Continuous open diameters of the micro-passages have a relatively straight flow path that reduces pressure drop relative to the random arrangement of other frits while still providing the desired containment.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of application Ser. No. 09/385,163 filedAug. 30, 1999, now U.S. Pat. No. 6,357,484, which application claimspriority from Provisional Application Serial No. 60/098,457 filed Aug.31, 1998, the contents of which are hereby incorporated by reference inits entirety.

FIELD OF THE INVENTION

This invention relates to the making of microporous structures withmicro-channels that are particularly useful as containment devices.

BACKGROUND OF THE INVENTION

In capillary electrochromatography (CEC) and related analytical methods,there are currently no repeatable techniques or materials which ensurethat the medium inside the capillary does not leak. There is a need,especially in the separation sciences, for fluid-permeable containmentdevices to retain fluids or packings or to filter particles from flowingstreams of gas or liquid Common containment devices for this purposeinclude fiberglass packings, screens, and bonded particles, typicallyreferred to as frits.

There are many different methods of making frits but most techniquesemploy the consolidation of small particles by sintering or meltingcompressed particles of a known size together. In one typical method, anappropriate material is ground up into small pieces and screened for aselected size range of particles. The particles are then compressedtogether in a mold and heated. The objective is to apply sufficient heatto fuse the particles together but not to melt the particles. Generally,the heating cycle is moderately complex in that there is a temperatureprofile of several different temperatures and times that give the bestresults After heating, the mold is removed and the resultant maze ofmaterial is then further processed by machining to trim the edges and/orwelded or glued to an appropriate substrate. Another approach usesfilaments of a given diameter and length that are randomly arranged,compressed, and fused together. The materials that are common to fritmanufacture are both metals and plastics

The present art in this type of frit manufacture is to a) size theparticles or strands, b) determine the amount of compression needed inthe mold, and c) determine the temperature cycle to produce restrictivepaths that have a nominal diameter of distribution. This means that thevoid space within these matrices have a consistent cross-sectionalshape. The greater the void space relative to the total cross-sectionalvolume, the better the frit. The narrower the pore diameterdistribution, the better the frit, and the more consistent the pathlength of the pores, the better the frit. The technology seems to bebased more on statistics than on rigorous mechanical design since it isimpossible to position millions of particles or filaments exactly insome geometrical pattern. Chaos theory appears to be the primary meansof predicting performance.

Screens provide a containment device that serves as an alternate tofrits but screens generally have a lower limit of performance based onthe size of the wire or filament used. This lower limit is probably inthe range of 25 to 125 μm and is established by the tensile strength ofthe filament and its ductility which is needed in the weaving process(over and under lapping in the loom). The pores or holes created by ascreen using very small wire approaches the diameter of the wire and theopen area of the screen for small holes is less than 50%. However,screens offer low back pressure compared to frits since screens areplanar in construction and frits derive their functionality fromthickness.

Neither the frit nor the screen offers an ideal structure for thecontainment of a packing or for providing a particle filter inapplications that require small hole or pore sizes, particularly for apacked capillary column as used in either liquid chromatography (LC) orcapillary electrophoresis (CE). The frit, because of the convolutedroute of the pore including paths that contain lateral translations, hashigh back pressure. While a screen has low back pressure, the screen hasa lower limit on “pore” size.

It is an object of this invention to provide a containment structurethat reduces the pack pressure relative to a frit structure while notlimiting the minimum size of the micro-passages to those associated witha screen.

It is a broader object of this invention to provide a microporousstructure having low pressure drop and pore diameters of 5 μm or less.

SUMMARY OF THE INVENTION

This invention accomplishes these objectives with a microporousstructure that defines a plurality of singular micro-passages thatextend along the axial length of the structure. The plurality ofsingular micro-passages provide low restriction flow paths for the fluidthrough the structure. Each singular micro-passage can provide a directflow path through the structure with a length that equals that of thestructure and is free of obstructions The walls that define themicro-passages have a relatively straight configuration that permitsextension of wall length without limiting the minimum diameter of thewalls or disproportionately increasing pressure through the passages.Increasing the wall length increases the overall strength of thestructure to pressure imposed by the fluid or packing.

The structure achieves tight dimensionality of the micro-passages whichcontributes to the dramatic reduction in back pressure that has beenachieved. This dramatic reduction in back pressure is achieved eventhough the thickness of the structure may exceed that of a conventionalcompressed particle frit.

The structure is readily manufactured using a modified form of thetechnique common to glass drawing. The method involves the fabricationof a number of tubes in “macro” to provide a preform which is then drawndown into an extended length of the structure. Lateral slicing of theextended structure supplies wafers of the structure in desired lengthsfor particular applications. The technology employed to fabricate thestructure is similar to the drawing of polyimide coated fused silica oroptical waveguide fibers but with distinctly different drawingconditions. A key difference is the use of a low temperature in thedrawing furnace compared to either capillary tube drawing or opticalwaveguide drawing. In drawing the structure of this invention, thefurnace is heated to a temperature that is just sufficient to draw thepreform. The viscosity of the preform is kept high, near the low end ofthe softening temperature of the glass, resulting in a tractive forcebeing required to draw the filament from the preform. This is counter tothe typical process of drawing optical waveguide where the preform will“drop” due to gravity alone.

The advantage of the formed structure is very high porosity (open spaceto structure), very low back pressure because the “pore” path isstraight with no obstructions and statistically the “pore” diameterfalls within a very narrow range. Furthermore, there is no lower rangeon “pore” diameter. Theoretically, the “pore” diameter can approach thesize of the molecules that make up the glass. For example, if fusedsilica were employed, the “pore” diameter could approach a fewnanometers. Overall, this manufacturing process is suitable formanufacturing structures with multiple micro-pores, also referred to asmulticapillaries that can have outer diameters of from severalmillimeters to less than 100 μm. Internal bore diameters of themicro-passages provide pores that can range in size from several hundredmicrometers to less than 10 nm. The “pore” field, i.e. the area definedby the outer diameter of the micro-passages, can have diameters ofseveral millimeters to less than 10 nm. The number of pores can rangefrom 7 to several thousand and possibly as high as 100,000. Thisapproach has been found to be very flexible—meaning that the outer sizecan be varied over a large range, the bores can be varied over an evenlarger range, and the number of bores within a structure does not seemto have an upper limit.

The preform assembly is typically in the form of a tube that defines theouter circular wall and that retains the internal micro-passage area ofthe pore field. In most applications, it is preferred that the regularlyrecurring shape of the capillary cross-section also define capillariesof the same size. The regularly recurring shape of the capillarycross-sections is typically round but may take on oval and rectilinearshapes as well.

A useful feature of this invention is the provision of the internalmicro-passages having a regularly recurring shape. The internal openarea defined by regular micro-passages, those with cross-sections in theform of the same regularly recurring shape, will equal at least 80% andmore preferably at least 90% of the total internal open area in the porefield. Any remaining flow area through the structure is typically in theform of irregular micro-passages having individual cross-sectional areasthat are less than the individual cross-sectional areas of the regularmicro-passages The relatively small diameter of the irregularmicro-passages minimizes the detrimental effect that the presence of theirregular capillaries may have on the different applications for thestructure of this invention. The preferred structure of this inventionprovides uniform micro-passages that virtually eliminate the presence ofirregular micro-passages. In this preferred structure, the internal openarea defined by regular micro-passages will equal at least 95% and morepreferably at least 99% of the total internal open area of the porefield.

This consistency in the manufacturing process yields a substitute forconventional frits and packings wherein each microporous structure froma particular draw is characteristically identical to the otherstructures. In addition, aside from reducing and simplifying capillarypreparation, the ease of assembly for the end user further promotes therepeatability of multiple analyses. Together, the form and employment ofthe microporous structure ensures the results of each analysis are notinfluenced by the containment device or the individual's unique methodof capillary preparation.

Certain criteria have been found to be useful in producing themicro-passages of this invention. First the inner tubes in the preformgenerally have a minimum wall thickness below which the inner tubes willdistort, which in the completed draw is a wall thickness to holediameter of at least 1:5. Furthermore, all of the inner tubes should bevery consistent in bore and wall thickness or else distortion will occurin the shape of the finished hole and/or the pattern of the holes willbe distorted. Moreover, the wall of the outer tube should havesufficient thickness to provide the necessary surface tension for theassembly to collapse or “draw” together during the forming process. Therequired minimum thickness seems to be dependent on the size of thestructure with thicker outer tubing walls generally providing betterstructures. Another useful parameter when seeking to minimize irregularchannel formation is temperature uniformity during the drawing process.It has been found that the drawing apparatus should not permitsubstantial temperature variations during the drawing operation.Temperature variations should be held to less than 5° C. over the lengthof the draw.

In some cases, the occurrence of irregular micro-passages may be reducedby packing conduits with a thicker wall section toward the outside ofthe preform assembly. Wall thickness of the conduits may be increasedincrementally with increasing distance from the center of the tube.However, in some assembly draws, particularly as the number of packedconduits increases, minimum irregular micro-passages were produced byuniformly increasing the wall thickness of all of the conduits in one ortwo of the outermost rows. The wall thickness selection of the conduitsto minimize irregular passage formation will vary with size and numberof the desired micro-passages as well as the material of the assembly.The additional conduit wall thickness is preferably maintained bydecreasing the inside diameter of the conduits. Surprisingly, it hasbeen observed that the conduits with increased wall thickness tend toproduce slightly larger passages than the passages produced by conduitswith relatively thinner walls.

In addition, when the structure will contain a small number of pores,typically less than 200 micro-passages, and the structure is formed fromcircular tubes, it is advantageous to arrange the smaller individualtubes of the preform to satisfy certain requirements when placed withina larger tube that supplies the outer wall of the structure. In sucharrangements, the multiple tube assembly of the preform should besymmetrical and the total number of tubes should approximate the maximumnumber of smaller uniform circles that should fit within a larger outercircle. This relationship has been found to provide the most effectivepacking arrangement. Jacques Dutka, in Machinery Journal, October 1956,gives the maximum number of small circles that may be packed into alarger circle for a number of different packing arrangements Based onthese formulas, it has been found that for this invention the typicalnumber of total passageways in a given number of passageway rings isbest given by the formula for maximizing circles as presented in theforegoing reference. Therefore, where the desired arrangement for roundconduits is as an assembly of rings about a central tube, the number ofconduits in the assembly is determined by:

N=3n ²+3n+1;

where,

N=the total number conduits, and

n=the number of rings of conduits around the central conduit.

Where all of the inner conduits have the same outer diameter, thepreferred inner diameter of the outer tube is calculated in terms of a“K” factor defined by the above reference. Accordingly, the outer tubehas an inner diameter “D” determined by the outer diameter “d” of theinner conduits where:

D=K*d

The factor K varies mathematically with the number of inner conduits.Values for K are set forth in the above reference. Examples of specific“K” values are set forth in Table 1 for arrangements that wrap rings ofconduits around a central conduit.

TABLE 1 # of Inner I.D. of # of Inner I.D. of Conduits Outer TubeConduits Outer Tube 2-7 3 122-127 13  8-13 4.465 128-139 13.166 14-19 5140-151 13.490 20-31 6.292 152-163 14.115 32-37 7.001 164-169 14.85738-43 7.929 170-187 15 44-55 8.212 188-199 15.423 56-61 9.001 200-21116.100 62-73 9.718 212-223 16.621 74-85 10.166 224-235 16.875 86-91 11236-241 17 92-97 11.393 242-253 17.371  98-109 11.584 254-262 18.089110-121 12.136

When the number of pore forming tubes exceeds several hundred, meetingthe approximation of circles within circles does not seem to make anydifference However, it is still useful to maintain a relatively tightpacking of the smaller tubes within the outer tube. Furthermore, it hasbeen specifically found that minimizing the inner diameter of the outercontainment tube for the number of pore forming conduits containedtherein dramatically increases the volume of regular capillaries formedduring the drawing process.

The structure may be formed from any ductile material that is suitablefor drawing when softened to a plastic state. The only apparentrestraint suitable material is that the material needs to have drawingproperties which afford a reasonably high viscosity at its softeningpoint. Thus, both inorganic glasses and many plastics would be suitableand possibly some metals if they meet the viscosity criteria.

Prior to drawing, the conduits in the tube and conduit preform willpreferably have a diameter in a range of from 0.3 to 3 mm and a wallthickness of from 100 μm to 1 mm. The thickness of the outer tube willusually average from 1 to 5 mm.

Ductile glass materials have been found to be most suitable forproduction of the structure by the known methods of fabrication.Suitable glass material include lead silicate, borosilicate,conventional glasses (soda lime silicate), and other forms of highpurity silica such as quartz or fused silica. A particularly preferredglass material is an alumino-silicate. Glass drawn containmentstructures of this invention may be an order of magnitude thicker thanits metal or polymer compressed frit equivalent and still have lowerback pressure. It should also be noted that these glass drawn structureswhen used as frits have exceptional retaining power for packedcapillaries because of their length combined with the high compressiveloading glass can tolerate.

Accordingly, in a broad embodiment, this invention is a microporousstructure defined by a plurality of singular channels. The structurecomprises an axially extended outer wall surrounding an open area. Theopen area extends continuously over the length of the outer wall betweenopposite faces of the structure that are bordered by the ends of theouter wall. The faces are transverse or substantially transverse to theaxis about which the outer wall extends. The outer wall surrounds aplurality of singular micro-passages that have a maximum diameter notgreater than 25 μm with a maximum diameter of 5 μm being preferred and amaximum diameter of 2 μm being particularly preferred. Inner walls ofthe structure define the micro-passages. The inner walls extendcontinuously between the opposite faces of the outer wall to define atleast a portion of the open area and to substantially inhibit fluidcommunication between the micro-passages. Typically, the inner wallswill have a thickness that is less than half of the thickness of theouter wall.

In another embodiment, this invention is a method of forming amicroporous structure. The microporous structure is of the type thatincludes an axially extended outer wall surrounding a plurality ofsingular micro-passages that are defined by internal walls and thatextend along the axial length of the outer wall. The method inserts aplurality of conduits into a surrounding tube to form a tube and conduitassembly wherein the conduits have relatively small internal andexternal diameters relative to the tube. Sealing the common openings ofthe conduits about one end of the tube and conduit assembly forms adrawing preform having a closed end about which all conduits are sealedfrom fluid flow and an opposite open end about which all conduits areopen for fluid flow. The method requires heating of the drawing preformto a softening temperature that permits plastic flow of the drawingstock under an axial traction force but inhibits plastic flow of thedrawing stock under its own weight. Simultaneous drawing of the preformby application of the axial tractor force while maintaining the preformat the softening temperature and restricting fluid flow from the openend reduces the interiors of the conduits to a micro-passage size whilepreventing collapsing closure of the conduit interiors. Collection of amicroporous structure from the drawn drawing stock provides a structurethat has a plurality of singular micro-passages defined by internalwalls and substantially equal in number to the number of conduits.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic representation of a scanning electron microscopeimage taken across a transverse section of the microporous structure ofthis invention.

FIG. 2 is a section view of the microporous structure of this inventionretained in a sleeve at the end of capillary tube.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIG. 1 shows a cross-section of a typical microporous structure of thisinvention as recorded by a scanning electron microscope. The schematicrepresents the structure enlarged by 500 X. The micro-porous structure10 has an outer wall 11 defining an inner diameter 12 that encircles aplurality of internal walls 13. Internal walls 13 define a plurality ofsingular microporous passages 14 that provide an open area of a porefield bordered by inner diameter 12. The actual micro-passages have ahigh degree of uniformity and their total open area equal about 28% ofthe pore field. A high degree of integral bonding is created between thewalls separating the micro-passages.

The structure represented by FIG. 1 contains a total of 599micro-passages. The structure represented by FIG. 1 was formed using apreform assembled in accordance with packing approach that employs thepreviously defined equation, N=3n² +3n+1, to fill the circular inside ofthe large tube with smaller individual circles that initially define thepore forming conduits and to set the inner diameter of the outer tubewith the relationship D=K*d. The first several layers formed by therings of conduits approximate a hex pack configuration but as the layersof rings get larger (n>6) the layers appear to form a circle with somevoid space

As an example of a forming technique for the capillary tubes of thisinvention, the multi-capillary represented by FIG. 1 was formed by thefollowing method. The outer tube and 217 inner conduits had thefollowing properties.

outer tube I.D./O.D. 12.9/15.3 mm inner tube I.D./O.D.  400/790 μm glassmaterial aluminosilicate glass glass melting point 1120° C.

The smaller tubes protrude past the outer tube by approximately 25 mmand have their top ends capped to inhibit gas flow in the tubing. Thisprevents the tubes from collapsing and forming a solid rod during thedrawing process. The structure for the drawing stock is assembled onerow of conduits at a time using glue or rubber bands to hold each row inplace. The assembly is mounted in the drawing tower and allowed toslowly equilibrate at the softening temperature of the glass. Thisbegins to establish the surface forces on the initial part of theassembly and corrects for slight packing errors. The tip of the preformis then dropped and a tractor is used to draw the preform structure fromthe furnace.

The drawing furnace was operated in the following manner:

top feed rate 14.7 mm/min bottom feed rate   8 M/min carrier gas flow(He)30% Δr 70%   6 L/min furnace temperature 983° C.

Capillaries of other sizes may be produced in varying numbers using theformula or a suitable packing arrangement. The finished size of themicro-passages will usually be in a size range of from 0.5 through 5 μm.The outer wall of the structure can vary in size from 2 mm to 0.1 mm.

While not confirming any particular theory about the manner in which themethod forms the tubes, it is believed that during the drawing processof the assembly, surface tension of the outer structure forces theassembly to conform to its least geometric energy state, relying on asymmetrical distribution of surface tensions of both the outer surfaceof the assembly and the inner surfaces of the bores coupled with borepressurization to form a uniform pattern of holes with no void space.

Some additional forming techniques and material properties can improvethe uniformity and performance of the microporous structure. Drawing thestructure from conduits that themselves having very uniform bores andwall enhances the uniformity of the resulting structure. Uniformity ofthe individual conduits may be enhanced by drawing the starting conduitsdown in several stages from large conduits. Uniformity of the resultingcapillaries also improves as the alignment of the conduits in thedrawing stock becomes more parallel.

The microporous structure of this invention is suited for chromatographyapplications including the CEC arrangement of the prior art. FIG. 2shows a typical connection arrangement that uses microporous structureof this invention as a frit. An end 21 of a connector 20 in the form ofa fused silica sleeve retains an end 22 of capillary tubing 24 incontact with the microporous structure 26. Typical dimensions for thefused silica sleeve include an outer diameter (A) of 1400 μm, an innerdiameter (B) of 370 μm, and a length of 3300 μm. Structure 26 has anoutside diameter of 365 μm, a pore field diameter (C) of 125 μm thatcontains 599 micro-passages having an average diameter of 2.9 μm, and alength of 800 μm. A suitable detection or assembly may communicate withthe outer end of the structure 36 through end 28 of connector 22.

The connection is assembled by placing the structure over the end of thecapillary and inserting the capillary into the sleeve with the capillarybottomed out against the microporous structure An appropriate bondingagent such as a UV curing acrylate may be used to retain the capillaryand the structure in the sleeve.

In addition to its use as a replacement for frits and screens, themicroporous structure of this invention has a variety of applications.Its use as a flow restrictor for regulating the discharge of hazardousfluids presents a simple application for the assembly outside the fieldof chromatography In terms of broad applications, the micro-passages mayserve as mini-conduits for retaining, conveying, or separating fluids.

The structure provided by this also provides unique length-to-diameterproperties. The aspect ratio (L/D ratio) for the conduit structure ofthis invention provides extremely long length relative to the smalldiameters of the pores or micro-passages. A draw of the structure with alength of only 10 mm can provide 0.5 μm pores with an aspect ratio of20,000. The same length draw to obtain 10 nm pores will provide anaspect ratio of over one million. Therefore, the structure of thisinvention can provide long relative path lengths in a very short device.

What is claimed is:
 1. A method of forming a microporous structurecomprising an axially extended outer wall that surrounds a plurality ofsingular micro-passages defined by internal walls and wherein themicro-passages extend along the axial length of the outer wall, themethod comprising: a) inserting a plurality of conduits into asurrounding tube to form a tube and conduit assembly wherein theconduits have relatively small internal and external diameters relativeto the tube; b) sealing the common openings of the conduits about oneend of the tube and conduit assembly to form a drawing preform having aclosed end about which all conduits are sealed from fluid flow and anopposite open end about which all conduits are open for fluid flow; c)heating the drawing preform to a softening temperature that permitsplastic flow of the drawing stock under an axial traction force butinhibits plastic flow of the drawing stock under its own weight; d)simultaneously drawing the drawing preform by application of a tractorwhile maintaining the preform at the softening temperature andrestricting fluid flow from the open end to reduce the interiors of theconduits to a micropore size while preventing collapsing closure of theconduit interiors; and, e) collecting a microporous structure from thedrawn drawing stock that has a plurality of singular micro-passagesdefined by internal walls and substantially equal in number to thenumber of conduits.
 2. The method of claim 1 wherein drawing of thepreform reduces the diameter at the open end of the preform upstream ofthe open end of the preform, restricts gas flow out of the interiors ofthe conduits, and thereby provides the restriction to fluid flow at theopen end.
 3. The method of claim 1 wherein the tube and conduit assemblycomprises a glass material.
 4. The method of claim 1 wherein the tubeand conduit assembly comprises an alumino-silicate glass.
 5. The methodof claim 1 wherein the tube and conduits have a round cross-section. 6.The method of claim 5 wherein prior to drawing the tubes in the tube andconduit assembly, the conduits have a diameter in a range of from 0.3 to3 mm and a wall thickness of from 100 μm to 1 mm.
 7. The method of claim1 wherein the number of conduits in the assembly does not exceed 200conduits and the conduits are arranged in the assembly as rings about acentral conduit and the number of conduits in the assembly is determinedby the following formula: N=3n ²+3n+1; where, N=the total numberconduits, and n=the number of rings of conduits around the centralconduit.
 8. The method of claim 7 wherein the conduits are arranged inthe assembly as rings about a central conduit and the number of conduitsin the assembly is determined by the following formula: D=K*d whereD=the inner diameter of the tube, d=the outer diameter of the conduits,and K=the factor for determining the minimum diameter of a circle thatcan retain the number of inner conduits in an arrangement with a centralconduit.